Treatment of textile materials



Patented Dec. 27, 1949 FICE TREATMENT OF TEXTILE MATERIALS Henry Charles Olpin and Alexander James Wesson, Spondon, near Derby, England, assignors to Celanese Corporation of America, a corporation oi Delaware No Drawing. Application February 18, 1947, Se-

rial No. 729,404. In Great Britain March 4,

6 Claims.

This invention has relation to the tinting of textile materials, and more particularly to that of materials having a basis of cellulose acetate or other organic derivatives of cellulose.

It is frequently desired to provide for the identification of textile materials, e. g. filaments, fibres, yarns and the like, throughout one or more processing operations by a means which does not permanently affect the character or appearance of the materials. A method which is commonly adopted for this purpose involves the fugitive tinting of the materials with dyestuffs or pigments which can readily be removed from or rendered permanently colourless on the materials. Various acid dyestuffs have been proposed as tinting agents for materials of cellulose acetate or other organic derivatives of cellulose, but it has been observed that, while satisfactory under a variety of conditions, these tinting agents occasionally become fixed on the materials under certain treatments so that they are not removed from the materials by a soap scour. Such fixation frequently occurs, in particular, when the tinted materials are subjected to a steaming operation, and the effect of steaming materials may be employed in assessing the value of any modifying treatment for reducing the tendency to fixation.

We have found that a substantial reduction or complete elimination of the risk of fixation of acid tinting dyestufis on organic derivative of cellulose materials may be obtained by applying the dyestufis in conjunction with Fixanol C. The latter isa quaternary ammonium salt containing a long chain alkyl group. It appears to form a salt or lake with the acid dye and further is capable of acting as a dispersing agent. It is of the class of compounds commonly known as cationic soaps or cation-active soaps." For example, although 15 minutes steaming at 220 F. of cellulose acetate material padded with a solution of Azo-Geranine 2G8 (Colour Index No. 31) containing 4 grams of the dyestuiT per litre leads to considerable fixation and consequent permanent colouration of the material, the same steaming treatment appliedto material padded with the dyestufi solution containing 8 grams per litre of Fixanol C gives a well tinted product which is substantially vfree from fixation since subsequent scouring yields a substantially uncoloured product. Similar results may be obtained with other acid tinting dyestuffs, e. g.

Naphthalene Fast Orange 2G8, Xylene Fast Green B (Colour Index No. 735) Disulphine Blue FFS, Coomassie Acid Blue RIS (Colour Index No. 208), and Brilliant Kiton Red B (Colour Index N0. 748) The proportions in which the cation-active soap may be employed cover a wide range. In general the amount of the soap should be at least equivalent to that oi the dyestuff present, i. e. it should serve to form the salt or lake of the total quantity of dyestufi present, and it is preferred to employ at least twice and up to four or five times the equivalent proportion, or even more. Such an excess of the cation-active soap appears to peptise the salt or lake which is formed with the equivalent proportion, and results in a solution which is very suitable for application to textile fibres and of which the colour yield on the fibre is very good.

The particular merits of the invention are illustrated, for example, by the tinting and lubricating of a 5,000 denier roving of cellulose acetate staple fibre with Azo-Geranine 2G8. One portion of the roving was tinted and lubricated with an emulsion comprising triethanolamine oleate and a lubricating oil, e. g. olive oil or arachis oil, in a solution of 4 grams per litre of the dyestuii, and another portion of the yarn was similarly tinted and lubricated with the same emulsion containing in addition 16 grams per litre of Fixanol C. Both tinted portions of the roving were steamed for 15 minutes at 220 F., and subsequently scoured for half an hour at 75 C. in a bath comprising 2 grams per litre soap, 0.59 gram per litre soda ash and 3 cos. per litre of a mixture of one part of xylene with 9 parts of Turkey red oil. The first portion showed considerable fixation of the dyestufi after scouring, whereas the second was then substantially colourless.

The dye/cationic soap complex is capable of employment in the presence of a wide range of concentrations of lubricating oil emulsions, and the invention may therefore be applied in conjunction with various lubricating treatments. Thus, for example, good aqueous emulsions may be formed from 2 gms. per litre Azo-Geranine 2G8 and 6 gms. per litre Fixanol C with 6, 12 and 18 gms. per litre arachis oil, and these may be employed for simultaneously tinting and lubricating cellulose acetate fibre, the tint resulting being completely removable after steaming.

It has been further found that the application of the acid tinting dyestutf in the presence of the cation-active soap yields remarkably improved shades on cellulose acetate or other derivative of cellulose materials. Thus a bright bluish red tint of excellent cover and freedom from tendency to sweal is obtained by the application of Azo-Geranine 2GS in conjunction with Fixanol C to cellulose acetate materials, whereas a drab red tint is obtained when a I simple aqueous solution of the dyestufl is employed. Very even and bright tints are also obtained in the presence of cation-active soap with other tinting dyestuffs as, for example, those listed above.

It has also been found that the dye/cationic soap complex or the cationic soap alone has the valuable property of acting as a de-electrirfying and lubricating agent so that cellulose ester or ether fibers carrying it can readily be subjected to textile operations, for example combing, carding, drafting, and spinning without trouble due to electrification of the fibres arising and without application of further de-electrifying or lubricating agents. Thus cellulose acetate staple fibre may be impregnated with a liquid made by dissolving 90 grams of Coomassie Acid Blue RLS and 2'10 grams of Fixanol C in 2 litres of water and diluting the resulting jelly-like mass to 9 litres with warm water. The fibre is then squeezed and hydroextracted so as to leave therein 60% of its weight of the liquid and is then opened up and dried. The product is cornflower blue in colour and can readily be worked up into yarn by the usual carding, gilling, combing, drawing and twisting operations without experiencing difliculties due to electrification or lack of lubrication. The colour can be completely removed by a short scour even after the material has been steamed for 15 minutes at 106 C. Similarly a fugitive tint may be produced, for example, by applying an aqueous medium containing 2 ms. per litre Azo-Geranine 2G8 and 6 gms. per litre Fixanol C.

In the foregoing description, reference has been made to the employing of Fixanol C for the purpose of the present invention. Other cationic soaps may be employed alone or in admixture with each other or with Fixanol C, for example. In particular, compounds can be employed which contain a long chain alkyl group or other hydrophobe group attached, directly or indirectly, to a basic radicle, particularly a quaternary ammonium group. Usually the compounds are used in the form of salts with acids, especially when the acid dye is in the form of the sodium or other 7 metal salt or the ammonium salt. Such compounds are for instance quaternary ammonium salts (e. g. chlorides, bromides, or sulphates) of which one of the radicles attached to the quaternary nitrogen atom is a long chain alkyl group (e. g. one containing a chain of at least 11 carbon atoms) for example the long chain alkyl pyridiniumsalts such as hexadecyl and octadecyl pyridinium bromide or sulphate. Another class of compounds useful for the purposes of the invention is the class of mono-acyl-unsymmetrical-N- dialkyl-alkylene diamines (the acyl radical being that of a fatty acid containing at least 12 carbon atoms) employed in the form of salts with acids or in the form of quaternary ammonium salts obtainable by the action of alkyl halides or alkyl sulphates, for example mono-oleylor mono-steeroyl-unsymmetrical-N-dimethyl-ethylene-diamine hydrochloride or metho-chlorlde or metho-sulphate.

Compounds of the above classes on the market, in addition to Fixanol C, are Sapamine KW, Lissolamine A, and Lissolamine V. Preferably the compound employed in conjunction with any particular dyestufi is such as to yield with the dye a clear solution in water.

The acid dye and the cationic soap can be applied to the materials in various ways, for example by padding or spraying the materials with aqueous preparations containing the dye and cationic soap. Further the dye and cationic soap can if desired, be appliel in conjunction with other substances for example in conjunction with softening agents, other lubricants and other de-electrifying agents. In this connection reference has already been made to the application of the dye and cationic soap in conjunction with triethanolamine oleate and an oil to a roving for the purpose of tinting the latter fugitively and simultaneously rendering it more amenable to further textile processing.

Theinvention is applicable to the tinting of organic derivatives of cellulose materials in the form of filaments, staple fibres, yarn and the like,

or in the form of woven, knitted or other fabric. The materials may be wholly composed of organic derivatives of cellulose, e. g. cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, ethyl cellulose, benzyl cellulose or other organic esters or ethers of cellulose, or may comprise organic derivatives of cellulose in admixture with other materials, e. g. wool or other natural protein materials, nylon and the like. The protein fibres such as wool can simultaneously be tinted so that the tint is fugitive particularly if acid conditions are avoided as is desirable even in the absence of any protein fibre. The tinted materials may be employed in various manufactures where ease of identification of the material is desirable or necessary. For example tinted staple fibre of a cellulose ester or ether may be mixed with untinted wool to produce a tinted mixture which can be worked up into yarns and fabrics from which the tint can readily be removed by scouring when it has served its purpose of identifying the staple fibre throughout the working up.

Having described our invention, what we desire to secure by Letters Patent is:

1. Method of simultaneously lubricating and applying a fugitive tint to textile materials having a basis of an organic derivative of cellulose so as to achieve a tint which remains fugitive even on steaming, which comprises applying to the material a tinting medium comprising an acid tinting dyestufi', water, a lubricating oil and a quaternary ammonium salt in which one of the radicles attached to the quaternary nitrogen atom includes an alkyl group having at least 11 carbon atoms in straight chain arrangement, the proportion of quaternary ammonium salt being sunlciently in excess of that chemically equivalent to the acid dye to bring the dye into solution and to emulsify the oil.

2. Method of simultaneously lubricating and applying a fugitive tint to textile materials having a basis of cellulose acetate so as to achieve a tint which remains fugitive even on steaming, which comprises applying to the cellulose acetate material a medium comprising an acid tinting dyestuff, water, a lubricating oil and a quaternary ammonium salt in which one of the radicles attached to the quaternary nitrogen atom includes an alkyl group having at least 11 carbon atoms in straight chain arrangement, the proportion of quaternary ammonium salt being suificiently in excess of that chemically equivalent to the acid dye to bring the dye into solution and to emulsify the oil.

3. Method of simultaneously lubricating and applying a fugitive tint to textile materials having a basis of cellulose acetate so as to achieve a tint which remains fugitive even on steaming, which comprises applying to the cellulose acetate 5 material a medium comprising an acid tinting dyestuff, water, a'lubricating oil and a quaternary ammonium salt having as one of the radicles attached to the quaternary nitrogen atom an alkyl group having at-least 11 carbon atoms in straight chain arrangement, the proportion of quaternary ammonium salt being sufliciently in excess of that chemically equivalent to the acid dye to bring the dye into solution and to emulsify the oil.

4. Method of simultaneously lubricating and. applying a fugitive tint to textile materials having a basis of cellulose acetate so as to achieve a tint which remains fugitive even on steaming, which comprises applying to the cellulose acetate material a medium omprising an acid tinting dye. stuff, water, a lubricating oil and a quaternary ammonium salt of a mono-acyl unsymmetrical N-dialkyl alkylene diamine with an acid, said acyl radicle being that of a fatty acid containing at least 12 carbon atoms in straight chain arrange ment, the proportion of quaternary ammonium salt being sufficiently in excess of that chemically equivalent to the acid dye to bring the dye into solution and to emulsify the oil.

5. Method of simultaneously lubricating and applying a fugitive tint to textile materials having a basis of cellulose acetate so as to achieve a tint which remains fugitive even on steaming, which comprises applying to the cellulose acetate material a medium comprising an acid tinting dyestuif, water, a lubricating oil and a quaternary ammonium salt formed from an alkyl ester of a mineral acid and a mono-acyl unsymmetrical N-dialkyl alkylene diamine, said acyl radicle being that of a fatty acid containing at least 12 carbon atoms in straight chain arrangement, the proportion of quaternary ammonium salt being sufliciently in excess of that chemically equivalent to the acid dye to bring the dye into solution and to emulsify the oil.

6. Method of simultaneously lubricating and applying a fugitive tint to textile materials having a basis of cellulose acetate so as to achieve a tint which remains fugitive even on steaming, which comprises applying to the cellulose acetate material a tinting medium comprising a preponderance of water, 'an acid tinting dyestuff, a lubricating oil and a quaternary ammonium salt in which one of the radicles attached to the quaternary nitrogen atom includes an alkyl group having at least 11 carbon atoms in straight chain arrangement, the proportion of quaternary ammonium salt being sufliciently in excess of that chemically equivalent to the acid dye to bring the dye into solution and to emulsify the oil.

HENRY CHARLES OLPIN. ALEXANDER JAMES WESSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,195,564 Finlayson Apr. 2, 1940 2,197,999 Dickey Apr. 23, 1940 2,207,696 Robinson July 9, 1940 FOREIGN PATENTS Number Country Date 358,202 Great Britain Oct. 8, 1931 OTHER REFERENCES Mosher: Permanent softening agen article in Amer. Dye Rep. for Sept. 4, 1939, pages 484-486. 

